CN102585044A - Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent - Google Patents
Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent Download PDFInfo
- Publication number
- CN102585044A CN102585044A CN2012100605363A CN201210060536A CN102585044A CN 102585044 A CN102585044 A CN 102585044A CN 2012100605363 A CN2012100605363 A CN 2012100605363A CN 201210060536 A CN201210060536 A CN 201210060536A CN 102585044 A CN102585044 A CN 102585044A
- Authority
- CN
- China
- Prior art keywords
- dendroid
- amide
- reaction
- group
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyamides (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a preparation method for a dendritic polyfunctional group reversible addition-fragmentation chain transfer (RAFT) reagent. The preparation method comprises the following steps of: undergoing an amidization reaction on trihydroxymethyl aminomethane and dendritic polyamide-amine of a terminated ester group to synthesize terminal hydroxyl group dendritic polyamide-amine; and under an alkaline condition, undergoing a reaction on carbon disulfide and the terminal ester group dendritic polyamide-amine to generate dendritic polyamide-amine sodium xanthate, and reacting with 2-halogenated carboxylic ester to obtain the xanthate-end-capped dendritic polyfunctional group RAFT reagent. The preparation method is easy and convenient; a product is easy to separate and has high yield; and the synthesized dendritic polyfunctional group RAFT reagent can be taken as a polyfunctional chain transfer reagent for adjusting and controlling RAFT of a vinyl monomer to synthesize a tree kernel star polymer, and the structure, molecular weight and distribution of the tree kernel star polymer can be controlled.
Description
Technical field
The present invention relates to a kind of method for preparing the reversible addition of dendroid polyfunctional group-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent), belong to polymer chemistry and papermaking chemical product technical field.
Background technology
The chemical structure of polymkeric substance and topological framework control are one of key content of polymer science area research.The molecular designing that appears as the special construction polymkeric substance of " activity "/controllable free-radical polymerisation technology provides new effective means.Reversible addition-fracture chain transfer (Reversible Addition Fragmentation Chain Transfer; RAFT) radical polymerization is a kind of new living radical polymerization technique that people such as Rizzardo proposed in 1998; Referring to Chiefari J; (Bill) Chong Y K, Ercole F, et al.Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer:The RAFT Process [J] .Macromolecules; 1998,31 (16): 5559-5562.Be about to have chain transfer agents such as two thioester compound of high chain transfer constant and ad hoc structure; Join in the traditional radical polymerization system that causes by AIBN, BPO etc.; Make Raolical polymerizable by uncontrollable become controlled, thereby realize regulation and control to polymer architecture and molecular weight and distribution thereof.Its reaction conditions is gentle, the suitable monomers scope is wide, implement polymeric method many (can adopt body, solution, emulsion, suspension polymerization etc.); It is exquisite and have the polymkeric substance of the various topological frameworks such as block, star, grafting of controllable molecular weight and narrow molecular weight distributions to synthesize various structures, is considered to one of " activity "/controllable free-radical polymerisation technology that has most industrial prospect.
The successful key of RAFT active free radical polymerization is to select the chain transfer agents (RAFT reagent) of suitable construction and chain transfer constant.RAFT reagent commonly used at present mainly contains dithio esters of gallic acid, xanthate class, dithiocarbamate and trithio esters of gallic acid; Its general structure is Z-C (=S) S-R; Wherein Z is an activating group, can activation C=S key, make its more easily and radical react; R is a leavings group, requires its easy homolysis and the radical monomeric polymerization of re-initiation effectively of the back formation of leaving away.The structure of RAFT reagent, performance and chain transfer constant depend primarily on the structure and the character of Z group (activating group) and R group (leavings group).
According to the RAFT polymerization mechanism, utilize RAFT reagent can synthesize the tree nuclear star shape polymkeric substance that has dendritic macromole and line polymer characteristic concurrently with dendritic structure.In order to obtain dendroid RAFT reagent, the peripheral active end group that normally will have the dendritic macromole of very regular branched structure and exhibiting high surface functional group carries out modification, on the branch unit basis, introduces two thioester substrates of corresponding number.Can be the R group of RAFT reagent also with the dendroid unit design as the Z group in the RAFT reagent, be called Z nuclear dendroid RAFT reagent respectively and examine dendroid RAFT reagent with R with the dendroid unit design.Dendroid polyamide-amide (PAMAM) is commercial at present dendritic macromole; Its molecular structure is highly branched; And have geometrical symmetry highly, and skin has a large amount of terminal functionality, and it is the effective way that obtains dendroid polyfunctional group RAFT reagent that its end group is modified.And, can regulate and control the reversible addition-fragmentation chain transfer free radical polymerization composite structure of vinyl monomer well and set nuclear star shape polymkeric substance accurately through appropriate design Z group and R group.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of method for preparing the reversible addition of dendroid polyfunctional group-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent).
Summary of the invention
The preparation method of the reversible addition of a kind of dendroid polyfunctional group-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent); It is characterized in that; At first adopt the Tutofusin tris and the dendroid polyamide-amide (Gn.5 PAMAM) of end ester group to carry out amidate action, synthetic terminal hydroxy group dendroid polyamide-amide (Gn.5 PAMAM-OH); Adopt the reaction of dithiocarbonic anhydride and terminal hydroxy group dendroid polyamide-amide then, synthetic dendroid polyamide-amide sodium xanthonate; Adopt the reaction of 2-halogenated carboxylic ester and dendroid polyamide-amide sodium xanthonate at last, make the end capped dendroid polyfunctional group of xanthate RAFT reagent.
Detailed Description Of The Invention
A kind of preparation method of dendroid polyfunctional group RAFT reagent, step is following:
1, adopt the Tutofusin tris and the dendroid polyamide-amide (Gn.5 PAMAM) of end ester group to react synthetic terminal hydroxy group dendroid polyamide-amide
Under magnetic agitation, in advance Tutofusin tris is dissolved in the DMSO 99.8MIN., get the dimethyl sulphoxide solution of Tutofusin tris, subsequent use;
The dendroid polyamide-amide (Gn.5 PAMAM) of end ester group is added in the reactor drum, is stirring, dripping DMSO 99.8MIN. in the logical nitrogen downhill reaction device, wait to hold the dendroid polyamide-amide of ester group to dissolve fully after, in reactor drum, add Anhydrous potassium carbonate.Then at the dimethyl sulphoxide solution that stirs and lead to the Tutofusin tris that dropping prepares in advance in the nitrogen downhill reaction device.Temperature in the reactor drum is risen to 25～70 ℃, under agitation react 6～120h.After reaction is accomplished, with the reacting liquid filtering disgorging.The liquid that obtains is carried out underpressure distillation, remove DMSO 99.8MIN. and byproduct of reaction methyl alcohol, obtain the pale oily liquids.With the oily liquids dissolving that obtains, add acetone with a small amount of zero(ppm) water, leave standstill and be cooled to 0～10 ℃ after the stirring.With the white powder solids washed with acetone of separating out and carry out vacuum-drying, promptly get terminal hydroxy group dendroid polyamide-amide (Gn.5PAMAM-OH);
The dendroid polyamide-amide of said end ester group (Gn.5 PAMAM); Be the finger tip number of ester groups be respectively 4,8,16,32 the 0.5th, 1.5,2.5,3.5 generation one of dendroid polyamide-amide, brief note is G0.5 PAMAM, G1.5 PAMAM, G2.5 PAMAM, G3.5 PAMAM respectively;
Tutofusin tris is (4～160) with the mol ratio of the dendroid polyamide-amide of end ester group in the above-mentioned reaction system: 1; The mol ratio of Anhydrous potassium carbonate and Tutofusin tris is (1～2): 1;
The terminal hydroxy group dendroid polyamide-amide Gn.5 PAMAM-OH that above-mentioned reaction makes is respectively 12,24,48,96 G0.5 PAMAM-OH, G1.5 PAMAM-OH, G2.5 PAMAM-OH, G3.5 PAMAM-OH for the terminal hydroxy group number.
2, the terminal hydroxy group dendroid polyamide-amide reaction of adopting dithiocarbonic anhydride and step 1 to make, synthetic dendroid polyamide-amide sodium xanthonate
In reactor drum, adding concentration is the sodium hydroxide solution of 5%～65% (weight percent), under agitation adds the terminal hydroxy group dendroid polyamide-amide that step 1 makes, and the dissolving back slowly drips dithiocarbonic anhydride in ice-water bath, stirring downhill reaction device.The temperature that drips in the conditioned reaction device of back is 15～45 ℃, reaction 1～24h.Reaction adds THF after accomplishing in reaction system, the yellow mercury oxide of separating out is also added THF with dissolved in distilled water more again it is separated out, and the yellow powdery solid that obtains promptly gets dendroid polyamide-amide sodium xanthonate through vacuum-drying;
The mol ratio of dithiocarbonic anhydride and terminal hydroxy group dendroid polyamide-amide is (4～192) in the above-mentioned reaction system: 1; The mol ratio of sodium hydroxide and dithiocarbonic anhydride is (1～2): 1;
The dendroid polyamide-amide sodium xanthonate that above-mentioned reaction makes is that sodium xanthonate end group number is respectively 12,24,48,96 dendroid polyamide-amide sodium xanthonate.
3, the dendroid polyamide-amide sodium xanthonate reaction of adopting 2-halogenated carboxylic ester and step 2 to make, the end capped dendroid polyfunctional group of preparation xanthate RAFT reagent
In reactor drum, add the dendroid polyamide-amide sodium xanthonate that step 2 makes, at ice-water bath, stir and add deionized water down, treat that dendroid polyamide-amide sodium xanthonate dissolves fully after, slow adding 2-halogenated carboxylic ester in reactor drum under agitation.Be 15～75 ℃ with the temperature adjusting in the reactor drum after dropwising, reaction 1～48h.With the yellow powdery solid of reacting liquid filtering, use the deionized water thorough washing again after reaction is accomplished, promptly get the end capped dendroid polyfunctional group of xanthate RAFT reagent through vacuum-drying with the collection generation;
Said 2-halogenated carboxylic ester is meant one of 2 bromopropionic acid methyl esters, 2-methyl chloropropionate, 2 bromopropionic acid ethyl ester, 2-chloropropionate, 2-isobutyl bromide methyl esters, 2-chlorine methyl isobutyrate, 2-isobutyl ethyl bromide, 2-bromo-butyric acid methyl esters, 2-chloro-butyric acid methyl esters;
The mol ratio of 2-halogenated carboxylic ester and dendroid polyamide-amide sodium xanthonate is (4～384) in the above-mentioned reaction system: 1;
The end capped dendroid polyfunctional group of the xanthate that above-mentioned reaction makes RAFT reagent is that xanthate end group number is respectively 12,24,48,96 dendroid polyfunctional group RAFT reagent.
Excellent results of the present invention is:
The present invention can synthesize the reversible addition-fragmentation chain transfer free radical polymerization of xanthate class polyfunctional group (RAFT) reagent quickly, and can control functional group's (xanthate end group) quantity of dendroid RAFT reagent well; And preparation technology is easy, product separate easily purifying, yield high, is easy to industriallization; The end capped dendroid RAFT reagent of synthetic xanthate can be used as the polyfunctional group chain-transfer agent; Reversible addition-the fragmentation chain transfer free radical polymerization of the especially non-conjugated vinyl monomer of regulation and control vinyl monomer; Synthetic tree nuclear star shape polymkeric substance, and structure, molecular weight and the distribution thereof that can regulate and control to set nuclear star shape polymkeric substance.
Embodiment
Below in conjunction with embodiment the preparation method of a kind of dendroid polyfunctional group of the present invention RAFT reagent is described further, but is not limited thereto.
Embodiment 1:
(1) under magnetic agitation, in advance the 15.98g Tutofusin tris is dissolved in the 30mL DMSO 99.8MIN., be put in the constant pressure funnel subsequent use.12.12g the 0.5th generation dendroid polyamide-amide (G0.5 PAMAM) is added in the 250mL there-necked flask, stirring, feeding under the nitrogen to wherein dripping the 30mL DMSO 99.8MIN..After treating that G0.5 PAMAM dissolves fully, in there-necked flask, add the 20.02g Anhydrous potassium carbonate.Stirring the dimethyl sulphoxide solution that reaches the Tutofusin tris that dropping prepares in advance in there-necked flask under the logical nitrogen with constant pressure funnel then.Temperature in the there-necked flask is risen to 45 ℃, under agitation react 96h.After reaction is accomplished, with the reacting liquid filtering disgorging.The liquid that obtains is carried out underpressure distillation, remove DMSO 99.8MIN. and byproduct of reaction methyl alcohol, obtain the pale oily liquids.With the oily liquids dissolving that obtains, add acetone with a small amount of zero(ppm) water, leave standstill and be cooled to 4～6 ℃ after the stirring.With the white powder solids washed with acetone of separating out and carry out vacuum-drying, promptly get terminal hydroxy group dendroid polyamide-amide G0.5 PAMAM-OH;
(2) in the 250mL there-necked flask, adding 34.3mL concentration is the sodium hydroxide solution of 35% (weight percent); The terminal hydroxy group dendroid polyamide-amide G0.5 PAMAM-OH that under agitation 19g step (1) is made adds wherein, and the dissolving back adopts constant pressure funnel to wherein slowly dripping 22.84g dithiocarbonic anhydride under ice-water bath, stirring fully.Dripping the temperature of regulating in the flask back is 25 ℃, reaction 8h.Reaction adds THF after accomplishing in there-necked flask; Again with dissolved in distilled water and add THF again it is separated out, it is 12 dendroid polyamide-amide sodium xanthonate that the yellow powdery solid that obtains promptly gets sodium xanthonate end group number through vacuum-drying with the yellow mercury oxide of separating out;
(3) the dendroid polyamide-amide sodium xanthonate that 19.36g step (2) is made adds in the 250mL there-necked flask; Under ice-water bath, stirring, add deionized water; After treating that dendroid polyamide-amide sodium xanthonate dissolves fully, under agitation to wherein slowly adding 22.04g 2 bromopropionic acid methyl esters.Temperature adjusting with reaction system after dropwising is 35 ℃, reaction 24h.After reaction is accomplished with reacting liquid filtering to collect the yellow powdery solid that generates, use the deionized water thorough washing again, promptly getting xanthate end group number through vacuum-drying is 12 dendroid polyfunctional group RAFT reagent.
Embodiment 2:
(1) under magnetic agitation, in advance the 17.42g Tutofusin tris is dissolved in the 35mL DMSO 99.8MIN., be put in the constant pressure funnel subsequent use.18.08g the 1.5th generation dendroid polyamide-amide (G1.5 PAMAM) is added in the 250mL there-necked flask, stirring, feeding under the nitrogen to wherein dripping the 40mL DMSO 99.8MIN..After treating that G1.5 PAMAM dissolves fully, in there-necked flask, add the 21.68g Anhydrous potassium carbonate.Adopt constant pressure funnel at the dimethyl sulphoxide solution that stirs and lead to the Tutofusin tris that dropping prepares in advance in there-necked flask under the nitrogen then.Temperature in the there-necked flask is risen to 45 ℃, under agitation react 106h.After reaction is accomplished, with the reacting liquid filtering disgorging.The liquid that obtains is carried out underpressure distillation, remove DMSO 99.8MIN. and byproduct of reaction methyl alcohol, obtain the pale oily liquids.With the oily liquids dissolving that obtains, add acetone with a small amount of zero(ppm) water, leave standstill and be cooled to 3～6 ℃ after the stirring.With the white powder solids washed with acetone of separating out and carry out vacuum-drying, promptly get terminal hydroxy group dendroid polyamide-amide G1.5 PAMAM-OH;
(2) in the 250mL there-necked flask, adding 24mL concentration is the sodium hydroxide solution of 40% (weight percent); The terminal hydroxy group dendroid polyamide-amide that under agitation 19.1g step (1) is made adds wherein, and the dissolving back adopts constant pressure funnel to wherein slowly dripping 18.27g dithiocarbonic anhydride under ice-water bath, stirring fully.Dripping the temperature of regulating in the flask back is 30 ℃, reaction 12h.Reaction adds THF after accomplishing in there-necked flask; Again with dissolved in distilled water and add THF again it is separated out, it is 24 dendroid polyamide-amide sodium xanthonate that the yellow powdery solid that obtains promptly gets sodium xanthonate end group number through vacuum-drying with the yellow mercury oxide of separating out;
(3) the dendroid polyamide-amide sodium xanthonate that 21.35g step (2) is made adds in the 250mL there-necked flask; Under ice-water bath, stirring, add deionized water; After treating that dendroid polyamide-amide sodium xanthonate dissolves fully, under agitation to wherein slowly adding 28.24g 2-isobutyl bromide methyl esters.Temperature adjusting with reaction system after dropwising is 35 ℃, reaction 36h.After reaction is accomplished with reacting liquid filtering to collect the yellow powdery solid that generates, use the deionized water thorough washing again, promptly getting xanthate end group number through vacuum-drying is 24 dendroid polyfunctional group RAFT reagent.
Embodiment 3: different is that step (1) adopts is the 2.5th generation dendroid polyamide-amide (G2.5PAMAM) like embodiment 1.
Embodiment 4: like embodiment 3, the mol ratio of Tutofusin tris and the 2.5th generation dendroid polyamide-amide (62.5 PAMAM) is 32: 1 in the step (1) that different is.
Embodiment 5: like embodiment 1, what step (3) that different is adopted is 2-chloro-butyric acid methyl esters.
Embodiment 6: like embodiment 2, the mol ratio of 2-isobutyl bromide methyl esters and dendroid polyamide-amide sodium xanthonate is 48: 1 in the step (3) that different is.
Embodiment 7: like embodiment 1, the mol ratio of dithiocarbonic anhydride and terminal hydroxy group dendroid polyamide-amide is 24: 1 in the step (2) that different is.
Claims (5)
1. the preparation method of the reversible addition of dendroid polyfunctional group-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent), step is following:
(1) adopt the Tutofusin tris and the dendroid polyamide-amide (Gn.5 PAMAM) of end ester group to react synthetic terminal hydroxy group dendroid polyamide-amide
Under magnetic agitation, in advance Tutofusin tris is dissolved in the DMSO 99.8MIN., get the dimethyl sulphoxide solution of Tutofusin tris, subsequent use;
The dendroid polyamide-amide (Gn.5 PAMAM) of end ester group is added in the reactor drum, is stirring, dripping DMSO 99.8MIN. in the logical nitrogen downhill reaction device, wait to hold the dendroid polyamide-amide of ester group to dissolve fully after, in reactor drum, add Anhydrous potassium carbonate.Then at the dimethyl sulphoxide solution that stirs and lead to the Tutofusin tris that dropping prepares in advance in the nitrogen downhill reaction device.Temperature in the reactor drum is risen to 25～70 ℃, under agitation react 6～120h.After reaction is accomplished, with the reacting liquid filtering disgorging.The liquid that obtains is carried out underpressure distillation, remove DMSO 99.8MIN. and byproduct of reaction methyl alcohol, obtain the pale oily liquids.With the oily liquids dissolving that obtains, add acetone with a small amount of zero(ppm) water, leave standstill and be cooled to 0～10 ℃ after the stirring.With the white powder solids washed with acetone of separating out and carry out vacuum-drying, promptly get terminal hydroxy group dendroid polyamide-amide (Gn.5PAMAM-OH);
The dendroid polyamide-amide of said end ester group (Gn.5 PAMAM); Be the finger tip number of ester groups be respectively 4,8,16,32 the 0.5th, 1.5,2.5,3.5 generation one of dendroid polyamide-amide, brief note is G0.5 PAMAM, G1.5 PAMAM, G2.5 PAMAM, G3.5 PAMAM respectively; The terminal hydroxy group dendroid polyamide-amide Gn.5 PAMAM-OH that reaction makes is respectively 12,24,48,96 G0.5 PAMAM-OH, G1.5 PAMAM-OH, G2.5 PAMAM-OH, G3.5 PAMAM-OH for the terminal hydroxy group number.
(2) the terminal hydroxy group dendroid polyamide-amide reaction of adopting dithiocarbonic anhydride and step (1) to make, synthetic dendroid polyamide-amide sodium xanthonate
In reactor drum, adding concentration is the sodium hydroxide solution of 5%～65% (weight percent), under agitation adds the terminal hydroxy group dendroid polyamide-amide that step (1) makes, and the dissolving back slowly drips dithiocarbonic anhydride in ice-water bath, stirring downhill reaction device.The temperature that drips in the conditioned reaction device of back is 15～45 ℃, reaction 1～24h.Reaction adds THF after accomplishing in reaction system, the yellow mercury oxide of separating out is also added THF with dissolved in distilled water more again it is separated out, and the yellow powdery solid that obtains promptly gets dendroid polyamide-amide sodium xanthonate through vacuum-drying;
The dendroid polyamide-amide sodium xanthonate that reaction makes is that sodium xanthonate end group number is respectively 12,24,48,96 dendroid polyamide-amide sodium xanthonate.
(3) the dendroid polyamide-amide sodium xanthonate reaction of adopting 2-halogenated carboxylic ester and step (2) to make, the end capped dendroid polyfunctional group of preparation xanthate RAFT reagent
In reactor drum, add the dendroid polyamide-amide sodium xanthonate that step (2) makes, at ice-water bath, stir and to add deionized water down, treat that dendroid polyamide-amide sodium xanthonate dissolves fully after, slow adding 2-halogenated carboxylic ester in reactor drum under agitation.Be 15～75 ℃ with the temperature adjusting in the reactor drum after dropwising, reaction 1～48h.With the yellow powdery solid of reacting liquid filtering, use the deionized water thorough washing again after reaction is accomplished, promptly get the end capped dendroid polyfunctional group of xanthate RAFT reagent through vacuum-drying with the collection generation;
Said 2-halogenated carboxylic ester is meant one of 2 bromopropionic acid methyl esters, 2-methyl chloropropionate, 2 bromopropionic acid ethyl ester, 2-chloropropionate, 2-isobutyl bromide methyl esters, 2-chlorine methyl isobutyrate, 2-isobutyl ethyl bromide, 2-bromo-butyric acid methyl esters, 2-chloro-butyric acid methyl esters; The end capped dendroid polyfunctional group of the xanthate RAFT reagent that reaction makes is that xanthate end group number is respectively 12,24,48,96 dendroid polyfunctional group RAFT reagent.
2. the preparation method of the reversible addition of dendroid polyfunctional group as claimed in claim 1-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent); It is characterized in that Tutofusin tris is (4～160) with the mol ratio of the dendroid polyamide-amide of end ester group in step (1) reaction system: 1; The mol ratio of Anhydrous potassium carbonate and Tutofusin tris is (1～2): 1.
3. the preparation method of the reversible addition of dendroid polyfunctional group as claimed in claim 1-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent); It is characterized in that the mol ratio of dithiocarbonic anhydride and terminal hydroxy group dendroid polyamide-amide is (4～192) in step (2) reaction system: 1.
4. the preparation method of the reversible addition of dendroid polyfunctional group as claimed in claim 1-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent); It is characterized in that the mol ratio of sodium hydroxide and dithiocarbonic anhydride is (1～2) in step (2) reaction system: 1.
5. the preparation method of the reversible addition of dendroid polyfunctional group as claimed in claim 1-fragmentation chain transfer free radical polymerization chain transfer agents (RAFT reagent); It is characterized in that the mol ratio of 2-halogenated carboxylic ester and dendroid polyamide-amide sodium xanthonate is (4～384) in step (3) reaction system: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210060536 CN102585044B (en) | 2012-03-09 | 2012-03-09 | Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210060536 CN102585044B (en) | 2012-03-09 | 2012-03-09 | Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102585044A true CN102585044A (en) | 2012-07-18 |
| CN102585044B CN102585044B (en) | 2013-10-30 |
Family
ID=46474347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210060536 Active CN102585044B (en) | 2012-03-09 | 2012-03-09 | Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585044B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876718A (en) * | 2012-09-21 | 2013-01-16 | 华东师范大学 | Gene transfection vector based on low-algebraic polyamidoamine and preparation method and application thereof |
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN112409541A (en) * | 2020-11-23 | 2021-02-26 | 扬州工业职业技术学院 | Petroleum drilling fluid additive and preparation method thereof |
| CN114276549A (en) * | 2021-12-21 | 2022-04-05 | 中海石油(中国)有限公司 | Anionic high-surface-activity organosilicon water purifier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591403A (en) * | 2009-06-18 | 2009-12-02 | 浙江大学 | The preparation method of reversible addition-fragmentation chain transfer emulsion polymerization |
| CN102020754A (en) * | 2010-10-29 | 2011-04-20 | 山东轻工业学院 | Preparation method of cationic dendrimer-star polymer papermaking additive |
-
2012
- 2012-03-09 CN CN 201210060536 patent/CN102585044B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591403A (en) * | 2009-06-18 | 2009-12-02 | 浙江大学 | The preparation method of reversible addition-fragmentation chain transfer emulsion polymerization |
| CN102020754A (en) * | 2010-10-29 | 2011-04-20 | 山东轻工业学院 | Preparation method of cationic dendrimer-star polymer papermaking additive |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876718A (en) * | 2012-09-21 | 2013-01-16 | 华东师范大学 | Gene transfection vector based on low-algebraic polyamidoamine and preparation method and application thereof |
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN105669912B (en) * | 2016-03-03 | 2018-03-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of method for preparing star-like poly carboxylic acid series water reducer |
| CN112409541A (en) * | 2020-11-23 | 2021-02-26 | 扬州工业职业技术学院 | Petroleum drilling fluid additive and preparation method thereof |
| CN112409541B (en) * | 2020-11-23 | 2022-12-16 | 扬州工业职业技术学院 | Petroleum drilling fluid additive and preparation method thereof |
| CN114276549A (en) * | 2021-12-21 | 2022-04-05 | 中海石油(中国)有限公司 | Anionic high-surface-activity organosilicon water purifier and preparation method thereof |
| CN114276549B (en) * | 2021-12-21 | 2023-02-07 | 中海石油(中国)有限公司 | Anionic high-surface-activity organosilicon water purifier and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102585044B (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585044B (en) | Preparation method for dendritic polyfunctional group RAFT (Reversible Addition-Fragmentation Chain Transfer) reagent | |
| RU2011109185A (en) | METHOD FOR PRODUCING DEPOSITED CALCIUM CARBONATE USING A LOW-CHARGED POLYMER CONTAINING ACRYLATE AND / OR MALEINATE | |
| US20110204289A1 (en) | Water Absorbing Resin Particle Agglomerates and a Manufactiring Method of the Same | |
| US9045567B2 (en) | Surfactant composition for emulsion polymerization | |
| EP3466991B1 (en) | Polymer, method for producing polymer and polymer flocculant | |
| CN107552008A (en) | A kind of method of corn cob fiber element based aquagel absorption heavy metal ion | |
| CN107082841A (en) | The high temperature preparation method of acrylic ester aquosity dispersion | |
| CN106674416B (en) | A kind of Fluorine-Containing Copolymer Emulsion and its synthetic method, application | |
| CN107141385A (en) | A kind of preparation method of low molecular weight brominated polystyrene | |
| CN103724555A (en) | Preparation method for thermoplastic elastomer | |
| CN102533467A (en) | Synergist for liquid detergents and concentrated liquid detergents | |
| CN108483605A (en) | A kind of preparation method of modified natural polysaccharide heavy metal chelating trapping flocculant | |
| CN106939160A (en) | A kind of high mineralization water quality clean fracturing fluid | |
| CN102002445B (en) | Washing powder and soap powder viscosity reduction synergist | |
| AU2011200867B2 (en) | Method for producing hydrophobically modified acrylic rheology modifiers | |
| CA2836718A1 (en) | (meth) acrylic acid-based copolymer | |
| CN103980418A (en) | Cationic waterborne organic fluorine acrylate polymer as well as preparation method and application of cationic waterborne organic fluorine acrylate polymer | |
| CN105713157B (en) | A kind of amphipathic organic silicon block copolymer and preparation method with pH responses | |
| CN105001379A (en) | Continuous preparation method of macromoleclar dispersant for comb type pesticide | |
| CN102924660B (en) | Preparation method for starch-modified acrylate resin | |
| Ki et al. | Dispersion polymerization of styrene using poly (4-vinylpyridine) macro-RAFT agent under UV radiation | |
| CN103626932A (en) | Potentiating agent for laundry detergent | |
| CN110590996A (en) | Reflux precipitation polymerization preparation method and application of sulfonic group-containing polymer microspheres | |
| CN110981774A (en) | Preparation method of RAFT (reversible addition-fragmentation chain transfer) agent with good water solubility | |
| CN102517894B (en) | Method for regulating and controlling silk graft copolymerization reaction on basis of hydrophobic and hydrophilic performance of free radicals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |